Organic sulfur compounds having fungicidal activity



My invention relates to esters of an organic aliphatic or aromatic acid with an alkyl Xanthoyl. parbi wLQLwith a dialkyl-dithiocarbamyl carbinol.v This is a continuation-in-part of US. application. Serial No. 827,692, filed'July 17, 1959," which relates to organic sulfur compounds having the. for'mulaz' inwhich R is a methoxy, ethoxy, isopropyloxyor a di-, methyl a'rnino or diethylamin'o, group and R is a methyl or phenyl group; and to a process forapreparingr these-: compounds, characterized in that eithera metal -alky1- xanthate. having the formula:

in which R is preferably methyl, ethyl or isopropyl, and Meis a metallic element (e.g... sodiurn, or.potas,sium 01 a metal .dialkyl dithiocarbamatehavingthe formula.

R b S 3 in which 'R is methyl 'or .ethyl andgMeis sodiurn-orpotassium; is reactedwitha chlor'omethyl ester of-a carboxylic acid, such as acetic-or benzoicyacid, of thefore mula:

R -COOCH Cl (4) in which R is methyl or phenyl. The above-mentioned 4 copending application alsorelatesto fungicidal compositions comprising substances of the afore-mentioned type.

I have'found that compounds having the'Fo'rmula"1,in which R bathe-"aforementioned meaning and R is a benzyl group ("-CI -I 'C H have a high fungicidal activity.

Objects of my application comprise compoundsghaying the Formula 1 in which:R has the above-mentioned meaning andR is ta benzyl group, .;a process for preparing them and the fungicidal compositions containing-Quezon more of said compounds, alone or in admixture with other active and/ or auxiliary substance.

The compounds ofimy invention areiobtainedbwreaacting chloromethylphenylaeetate :with a metal compound having the formula: 5

s (5)" in which R has the aforementioned meaning and Me is an alkali metal, such as sodium or potassium according to the equation: 7 R' i+S-'Me G1G'Hz O'OO CHg -C fl a. s i

R-( Js-0H2-oGooH,O@Hr MeCl The reaction is carried outin the P12881166'Ofqflllillfb; solvent capable of dissolving one ,orboth, reactants. As solvents, monohydricalcohol, ketones, ortheir mixturesmay be used Suitable temperatures .mayz ,VaIYnWlthiIlfairly wide limits, e.g. from 10 to 80 C. The dura- United States Patent O 3,156,717 Patentellqv- 10,4 94

tion of the reaction varies from 11, to 16 h0urs. ;,.It is 6.01 31; venient csometimes rto ruseaan .eXQess: of .-0ne of the 0 reagents overathez-stoichiometric. amount..;;:

The metal; halide formed as .av byproduct of .the rear. tion can be eliminated by;;filtering.or-byaaddingewater In :the :latter .case, theyinorganiorsalt anda-the .excess, 1, if any, of organic salt.are dissolved .therebyresulting in the simultaneous precipitation of the desiredaproductae The main. reaction: product: canialso be 1-isolatedtbygother known/methods... such as vconcentration, distillation ands-i, crystallization. Theafollowingaillustrating examplesirarem given :to betten illustrate the tpreparation; of .thegmaterialsg and are not meant to limit the scope of-the--invention.-

EXAMPLE-l p oromethyl, p suyl etatea e. a dsdrt a spensi n 2- o fi iumifil mflhyl. .d b ec b ma e .80 c a etone- An ,e h nn rz tt sv p ce, w p ec pitati mo s dium c ride... mix u e is r fluxed for ,haltamh pp a .1 t enl t;

to stand; for 15 hours The react on m xture is then p u ed into, 5 01 o .w temt p ec pi a e th s.. ;m. d is filtered under vacuum and washed with jwater 26% g. r f dim thyl ,d h qca bamylcarb nq p eny1ae ate,..h y1 ,7 ing ,the formula.

as a gray-white crystalline solid are obtained. Theproduct, after crystallization from methanol, hasea melting-w point-0f;9091-f C. S :calculated- '23.8;1%;'r,S found==l 23.44-23.1l4%i-- EXAMPLE 2 p et y p sny a et tet anadd d t a suspension of Y192 g. of potassium ,ethylxanthate in 1 50 cc. of acetone; an exothermicreaetiontakes place yvith precipitation of potassium chloride. The mixture is refluxedwfor 'half .arnhouraancl ris .rthenalefttto sstandrfor 15 hours. The reaction mixture is then=.poured-into l50 cc.:.- of H 0; the oil thus separated; is treated with cc. of methylene chloride and washed twice with H O (each time 50"cc.,). After drying on 02101 and removing the solventby-reduced pressure, 21 g. of ethylxanthoylcarbinol phenylacetate, having the formula:

are obtained .as,a clear yellow oil having: Dg filllil; n =1.5665.=.. '1 S calculated=23.'l3%; S found =22,7( 22.69%.

Substitution-Inf potassium methylxanthate or potassium isopropylxanthate for potassium ethylxanthate yields respectively corresponding .methyl or isopropylxantho'yl carbinol phenylacetate.

EXAMPLE 3 18.4 g. of chloromethylphenylacetate are added to a SUSPGQSlOJl'fiQf? 24.6. g. ;;of :sodium;,diethyldithiocarbamate in-1 iccmf acetone; tamexothermiczreaction takeseplacem with precipitation ofesodium chlorides; The:.mi tUr:.i fluxedt r. h l a rh ur a slis t nleftl s and f r hours. The reaction mi tureisthenpouredjnto 159 cc. ofwater; the oil thus separated is treated, with Z0 cc, of methylene chloride and washedtwicewith H20 .150; cc. each time). After drying on CaCl and evaporation of thesolvent under: reduced pressure,l 28: g. of.-diethyl .dithiocarbamyl-carbinol phenylacetate, having theformulazr.

CgHs.

are obtained as a slightly turbid oil having: D.R=l.167;

invention to be used as fungicides can, for example, have I the following compositions:

(l) 90 g. of dimethyl dithiocarbamylcarbinol phenylacetate, 6.8 g. lignin sulphite, 3 g. of expanded silica, 0.15 g. of kieselguhr, and 0.5 g. of wetting agent obtained by condensation of ethylene oxide;

(2) 50 g. of diethyl dithiocarbamylcarbinol phenylacetate, 40 g. of kieselguhr, 2 g. of expanded silica and 8 g. of-lignin sulphite.

In application, the aforementioned formulations are added to water in such amounts as to reach the desired concentration. A homogeneous dispersion, ready for use (nebulization of plants) is then obtained by simple mechanical agitation.

Evaluation of the Anti-Oidial Activity The method used for evaluating anti-oidial activity consists of nebulizing under standard conditions aqueous dispersions of the products to be tested on small tobacco plants of the Virginia Bright ard conditions. When the nebulized product deposited thereon has become completely dry, the test plants are infected by slight rubbing with leaves covered with oidium (Erysiphe cichoracearum). The determination of the infection is carried out by estimating the percent proportion of leaf surface area covered with oidium about :15 days after treatment and by comparing it with the infection of untreated controls. The following classes of degrees if intensity of infection were thus established, in increasing order of infection:

lno infection 2-considerable reduction of infection as compared with the untreated control (-20% against 70-90% 3evident reduction of infection as compared with the untreated control (30-40% against 70-90%) 4-slight reduction of infection as compared with the untreated control (50-60% against 70-90%) 5-infection as in the untreated control 'A sample of commercial colloidal sulfur was used as variety bred under standin mm. The known fungicide sodium pentachlorophenate was taken as a reference for comparison. The results are classified as follows:

0inhibition halo with diameter less than 1 mm. 1-inhibition halo with diameter less than 1-2 mm. 2-inhibiiton halo with diameter less than 3-4 mm. 3-inhibition halo with diameter less than 5-7 mm. 4inhibition halo with diameter less than 8-11 mm. 5-inhibition halo with diameter less than 12-15 mm. 6-inhibition halo with diameter less than 16-20 mm. 7inhibition halo with diameter less than 21-25 mm. 8inhibition halo with diameter greater than 25 mm.

TABLE 2 Dose, Alter- Asper- Peni- 84100. Product pernaria gillus cill. ell.

cent temtis niger toqucf.

Dimethyldithiocarbamylcarbinol phenylacetate 1 4 4 2 2 0. 2 4 4 2 2 0. 04 1 l 0 0 Ethyl xanthoylcarbinol phenylacetate 1 3 2 2 0 0. 2 3 2 1 1 0. 04 0 0 0 1 Diethyldithiocarbarnylenrbinol phenylacetate 1 4 0 1 0 0. 2 3 0 1 0 O. 04' 2 0 0 0 Sodium pentachlorophenate 1 7 6 7 5 0. 2 5 5 5 2 0. 04 2 1 2 1 (b Evaluation of the Capacity of the Products T o Inhibit Growth and Diflusion of Fungine Mycelium According to the Porcelain Cup Method reference of comparison.

TABLE 1 TABLE 3 Intensity Product Dose, of infection Dose, Alter- Aspcr- Peni- Sacc.

percent after 15 Product pernaria gillus cill. ell.

days cent tennis niger toque]. Dimethyldithloearbamyl carbinol phenyl- Dimethyldithioearbamylacetate 0.250 1 earbinol phenylaeetate. 1 6 4 3 3 0.125 2 0.2 6 4 1 2 0.050 4 0.04 2 1 o 0 Diethyl dithiocarbamylcarbinol phenyl- Ethylxanthoyl oarbinolacetate 0.0500 1 phenylaeetate 1 4 4 2 1 0.0260 1 0.2 3 3 1 0 0.0126 2 0.04 1 1 0 0 0. 0062 3 Dlethyldithioearbamyl- Colloidal sulfur 0.0500 1 carbinol pheny1acetate 1 4 2 3 0 0.0250 1 0.2 3 1 1 0 0.0125 2 0.04 2 0 0 0 0. 0062 3 Sodium pentachlorophenate. 1 7 6 6 5 0.2 6 5 5 2 I 0. 04 2 1 2 1 The fungicidal activity of the products according to the invention is illustrated by the following results obtained by standard laboratory methods.

(a) Evaluation of the Capacity of the Products To Inhibit Growth and Diffusion of Fungine Mycelium, After Absorption on Filter Paper, Evaporation of the Solvent, Resolubilization and Difiusion on Nutritive Agar-Agar (0) Evaluation of the Capacity to Inhibit Germination and Growth of Fungine Mycelium, of the Products Incorporated in the Nutritive Agar-Agar (Streak Method) The streak method allows the examination of products hardly ditfusible in solidagar-agar. By this method, the solution of the products is incorporated in the nutritive substrate, while the inoculation of the test fungus is carried out bymeans of streaks with suspension of spores. The reading of the plates is carried out after 72 hours and the growth of the fungi is evaluated by indexes defined as follows:

no difference in respect of water as a control 1-slight difierence in respect of water as a control 2colonies spread over all streaks 3s0rne colonies on some streaks 4no fungus growth (b) Evaluation of the Capacity to Inhibit Sundry Fungus Growths An aqueous dispersion of formulation 1 above was applied by nebulation under standard conditions on young kidney beans plants grown in part under artificial light, after drying of the fungicide film on the plants, the plants were infected with bean rust (Uromyces appendiculatus). A 0.1% aqueous dispersion of diethyldithiocarbamyl carbinol phenylacetate inhibited the infection, while a 0.25% aqueous dispersion of dimethyldithiocarbarnyl phenylacetate reduced the same infection to 2%, as compared with that of the untreated controls.

A 0.0125 aqueous dispersion of diethyldithiocarbarnyl carbinol acetate, applied by nebuiation under standard conditions on grapevine leaves placed in a Petri dish, inhibited the development of downy mildew (Plasmopara viticola) to 5% of that of the untreated controls.

A 0.5% aqueous dispersion of the same product, nebulized under standard conditions on broad bean leaves in Petri dishes, reduced to 5%, as compared to the untreated controls, the infection of chocolate spot on broad bean (Botrytis fabae), which Was seeded after complete drying of the product deposited on the leaves.

A 0.025% aqueous dispersion of the above product, doposited dropwise on glass slides, inhibited the germination of Alternaria tennis spores.

I claim:

1. A compound having the formula:

in which R is selected from the group consisting of meth- OX ethoxy, isopropoxy, dirnethylamino and diethylarnino groups, and R is benzyl (-CH C H 2. Dimethyldithiocarbarnylcarbinol phenylacetate.

3. Ethylxanthoylcarbinol phenylacetate.

4. Diethyldithiocarbarnylcarbinol phenylacetate.

References Cited in the file of this patent UNITED STATES PATENTS 2,907,786 Gundel Oct. 6, 1959 2,910,497 Meuly Oct. 27, 1959 2,943,972 Van der Kerk July 5, 1960 2,990,317 Jones et a1. June 27, 1961 

1. A COMPOUND HAVING THE FORMULA: 